Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
  • C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
  • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
  • C07C2521/04—Alumina
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • C07C2523/24—Chromium, molybdenum or tungsten
  • C07C2523/26—Chromium
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
  • C07C2523/74—Iron group metals
  • C07C2523/755—Nickel
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/56—Ring systems containing bridged rings
  • C07C2603/58—Ring systems containing bridged rings containing three rings
  • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
  • C07C2603/74—Adamantanes

Definitions

• the present invention relates to a process for the production of adamantane by dealkylation of alkyladamantanes.
• the hydrocarbon adamantane tricyclo-(3,3,1l decane, occurs in minute amounts in some petroleum fractions. It has been prepared synthetically by treating endotetrahydrodicyclopentadiene with Lewis acids (Friedel- Krafts catalysts), such as AlCl -HCl or BF 'HCl. The yields of this known process are relatively low amounting to 10-40% generally about based on the starting hydrocarbon (US. Patent 2,937,211, P. Schleyer, et al.; Org. Synth., 42, 8 (1963), orH. Koch, J. Franken: Brennstoif-Chem.
• the alkyl derivatives of adamantane can also be obtained by isomerization of perhydroacenaphthene, perhydrophenanthrene or perhydroanthracene, and generally from polycyclic aromatic hydrocarbons having three rings which are completely hydrogenated and having at least 12 carbon atoms (US. Patent 3,128,316). Isomerization of such hydrocarbons by treatment with Lewis acids proceeds readily even at 5 C. to +50 C. and results in high yields of polymethyladamantanes. Thus, for example, the yield of 1,3-dimethyladamantane, which is formed by isomerization of perhydroacenaphthene, is practically quantitative.
• alkyl derivatives of adamantane are not as valuable as is the unsubstituted adamantane itself which possesses exceptional physical and chemical properties. It can be used as intermediate for various purposes. Its derivatives are biologically active and can be used for the production of valuable drugs and insecticides, as well as in the production of various plastics. Up to now, however, an economical process for the production of unsubstituted adamantane has not been available.
• adamantane can be produced in almost theoretical yields by heating a monoor poly-alkyladamantane to a temperature of about 250-800 C. in the presence of hydrogen or a substance which yields hydrogen under the conditions of the process.
• the heat ing is carried out in the presence of a hydrogenating catalyst, thereby dealkylating said alkyladamantane.
• undesirable side reactions giving rise to tarry products and the detruction of the adamantane skeleton are reduced to a minimum.
• the procedure of the invention has the additional advantage that it can be carried out continuously, e.g., by using a continuous-flow apparatus.
• the readily available 1,3- dirnethyladamantane can be used.
• the reaction was carried out over a nickel catalyst containing 8.5% A1 0
• the reaction products were analyzed over the entire temperature range from 250 to 800 C. Methyl groups were split off over the entire temperature range. Between 250 and 300 C., the demethylation was slow, the main demethylation product being monomethyladamantane. With increasing temperatures, the second methyl group began to be split off more rapidly and the reaction product thus contained more adamantane at temperatures above 300 C. Above 400 C., adamantane was the main reaction product.
• the demethylation was accompanied by a side reaction, the decomposition of the adamantane skeleton which started at a temperature of above 500 C., thereby effecting the yield of adamantane.
• the preferred temperature range for the process of the invention is therefore between about 300 and 500 C.
• the dependence of the dealkylation on the catalyst was determined, using an Ni/Al O catalyst.
• the reaction was performed with a series of catalysts containing 5, 15, 31, 32, 37, 44, 48, 52, 91 and 97% nickel at a temperature of 410 C.
• the highest conversion was obtained with catalysts containing 30-50% Ni, the conversion of 1,3-dimethyladamantane to adamantane passing a maximum.
• the pure adamantane can be readily isolated from the crude reaction product by recrystallization from conventional solvents. Methyladamantane or other alkyladamantanes remaining after the separation of the adamantane from the crude product can be recycled into the process.
• a highly active catalyst can be produced by reducing a mixture of oxides or hydroxides of nickel and aluminum with hydrogen at elevated temperatures e.g., 300-400 C. preferably 350 C., thereby obtaining elementary Ni A1 0 catalysts.
• the Ni-content in such catalysts is in the range of 3050% by weight.
• other catalysts have been found effective in the dealkylation process of alkyl-adamantane, such as the metals of the Groups VI and VIII of the Periodic System,
• Co, Mo, and W are examples of materials which provide a large surface area at the reaction temperatures.
• other supporting materials which provide a large surface area at the reaction temperatures can be used, such as precipitated silica, aluminum-silicates, certain natural or synthetic zeolites, bentonites, kieselguhr and the like.
• monoor poly-alkyladamantanes contemplates generally lower alkyl-substituted adamantanes, preferably monoor po1y-, methylor ethyl-adamantanes, such as, l-methyladamantane; l-ethyladamantane; 1,3- dimethyladamantane; 1,3 dimethyl-S-ethyl-adamantaue, 1,3,5,7-tetramethyladamantane; 1,3-dimethyl ethyladamantane, and the like.
• the dealkylation can be carried out at normal pressures, as well as at super-atmospheric pressures, such as from 2-50 atm. gauge.
• the hydrogen is applied in a molar excess based on the alkyladamantane used. Generally, a molar ratio of alkyladamantane/ hydrogen in the range of 1-3 to 1-15 is appropriate. Advantageously, a molar ratio of between 1:5 and 1:10 is used, whereby a ratio of about 1:7 is preferred.
• hydrogen generating substances such as Water and the like can be used.
• the process of the invention is illustrated by the following examples: In carrying out the processes of the examples, a continuous-flow apparatus provided with a solid catalyst bed was used. The percent values in the examples are by weight. The composition of the reaction products was analyzed by gas-chromatography.
• Example 1 A mixture of vapors of 1,3-dimethyladamantane and hydrogen at a molar ratio of 1:7 was conducted under atmospheric pressure, at a volume rate of 1.32 mol 1,3- dimethyladamantane/h kg. catalyst at 417 C. over a solid nickel catalyst containing 37% Ni and 62.8% A1 0 and produced the following reaction product: 79.5% adamantane, 19.7% l-methyladamantane and 0.8% nonreacted 1,3-dimethyladamantane.
• the crude reaction product was dissolved in four weight parts of boiling tetrachloromethane. After cooling the solution to 20 C., pure adamantane having a melting point of 269 C. crystallized from the solution. By concentrating the mother liquor the remaining adamantane of about 95% purity (M.P. 265 C.) was obtained.
• Example 2 The procedure described in Example 1 was followed except that an industrial contact catalyst was used, which contained 48% Ni and 52% A1 0 The volume rate of 1,3-dimethyladamantane was 3.1 mol/h kg. catalyst. At 410 C., the reaction product contained 52.6% adamantane, 39.6% l-methyladamantane and 4.2% 1,3-dimethyladamantane.
• Example 3 The procedure of Example 1 was followed with the exception that l-methyl-adamantane was used as the compound to be dealkylated at 380 C.
• the reaction product contained 72% adamantane and 28% l-methyladamantane.
• Example 4 The procedure according to Example 1 was followed except that l-ethyladamantane was used as starting material.
• the reaction product contained 81.2% adamantane and 18.8% l-methyladamantane.
• Example 6 The procedure of Example 5 was followed except that 1,3,5,7-tetramethyladamantane served as the starting material.
• the reaction product contained 66.5% adamantane, 24.1% l-methyladamantane, 8.2% 1,3-dimethyladamantane and 1.2% 1,3,5-trimethyladamantane.
• Example 7 The procedure described in Example 1 was followed with the exception that the dealkylation was carried out at a pressure of 25 atm.
• the reaction product contained 82.4% adamantane and 17.6% l-rnethyladamantane.
• EXAMPLE 8 A mixture of gaseous 1,3-dimethyladamantane and hydrogen at a molar ratio of 1:7 was conducted at atmospheric pressure, at a volume of 1.29 mol 1,3-dimethyladamantane/ h kg. catalyst at 720 C. over a solid chromium catalyst containing 24.8% Cr O and 75.0% A1 0 and yielded the following reaction product: 60. 8% adamantane, 36.2% l-methyladamantane and 3% 1,3- dimethyladarnantane.
• Method of preparing adamantane which comprises reacting a member selected from the group consisting of monoand poly-alkyl derivatives of adamantane containing one to four carbon atoms in the alkyl groups thereof with hydrogen at a temperature of from 250-800 C. in presence of a dealkylating catalyst selected from the group consisting of Group VI and VII metals and their oxides supported on a solid carrier and recovering the adamantane thereby formed.
• Method according to claim 1 which comprises conducting said reaction at an elevated pressure.
• Method according to claim 2 which comprises conducting said reaction at a pressure of 0.1-300 atmospheres.
• adamantane derivative is a member selected from the group consisting of 1,3-dimethyladamantane, l-methyladamantane, l-ethyladamantane, 1,3-dimethyl-S-ethyladamantane and 1,3,5,7-tetramethyladamantane.

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Citations (2)

• 1966
  • 1966-12-27 NL NL6618212A patent/NL6618212A/xx unknown
  • 1966-12-27 DE DE19661568362 patent/DE1568362A1/de not_active Withdrawn
  • 1966-12-28 US US605232A patent/US3418387A/en not_active Expired - Lifetime
  • 1966-12-28 FR FR89072A patent/FR1513451A/fr not_active Expired
  • 1966-12-28 GB GB58002/66A patent/GB1123320A/en not_active Expired

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